WO2016158332A1 - Composition de résine et objet moulé obtenu à partir de celle-ci - Google Patents

Composition de résine et objet moulé obtenu à partir de celle-ci Download PDF

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Publication number
WO2016158332A1
WO2016158332A1 PCT/JP2016/057887 JP2016057887W WO2016158332A1 WO 2016158332 A1 WO2016158332 A1 WO 2016158332A1 JP 2016057887 W JP2016057887 W JP 2016057887W WO 2016158332 A1 WO2016158332 A1 WO 2016158332A1
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polymer
carbon atoms
group
mass
meth
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PCT/JP2016/057887
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English (en)
Japanese (ja)
Inventor
和起 河野
桑原　久征
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三菱瓦斯化学株式会社
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Application filed by 三菱瓦斯化学株式会社 filed Critical 三菱瓦斯化学株式会社
Priority to CN201680012002.XA priority Critical patent/CN107406654B/zh
Priority to EP16772215.6A priority patent/EP3279259A4/fr
Priority to JP2016551328A priority patent/JP6112264B2/ja
Priority to US15/535,580 priority patent/US10150865B2/en
Priority to KR1020177023343A priority patent/KR101898108B1/ko
Publication of WO2016158332A1 publication Critical patent/WO2016158332A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods

Definitions

  • the present invention relates to a resin composition and a molded body using the resin composition.
  • Polycarbonate resins are widely used in electrical and electronic equipment, OA equipment, optical media, automobile parts, building materials, etc. due to their excellent mechanical strength, heat resistance, electrical properties, dimensional stability, flame retardancy, transparency, etc. Yes.
  • Such polycarbonate resin is usually an interfacial method in which bisphenol A (aromatic dihydroxy compound) and phosgene are directly reacted, or transesterification reaction (polycondensation reaction) in the molten state of bisphenol A and diphenyl carbonate (carbonic acid diester). Manufactured by a melting method.
  • a molded body obtained from a polycarbonate-based resin produced using bisphenol A as an aromatic dihydroxy compound has insufficient surface hardness in applications that are used outdoors such as automobile headlamps, eyeglass lenses, and sheets. .
  • the surface hardness may be improved by providing a hard coat layer on the surface of the polycarbonate resin.
  • Patent Documents 1 and 2 describe resin compositions containing a polycarbonate resin and an acrylic resin having a specific range of molecular weight.
  • Patent Documents 3 to 7 describe resin compositions containing a polycarbonate resin and a (meth) acrylic copolymer.
  • Patent Documents 1 to 7 have difficulty in achieving both sufficient surface hardness and transparency in a molded product, or molding conditions are very narrow. Only under limited conditions, both surface hardness and transparency were compatible. Further, the resin composition proposed in Patent Document 8 also requires further improvements for various characteristics including surface hardness, transparency, and the like.
  • an object of the present invention is to provide a resin composition that can be molded under a wide range of molding conditions and can give a molded article having excellent surface hardness and transparency.
  • Another object of the present invention is to provide a molded product obtained from the resin composition and a blend of a plurality of (meth) acrylic polymers constituting the resin composition.
  • the present inventor has found that a polymer containing a (meth) acrylate unit having a specific skeleton and a polymer containing a methyl (meth) acrylate unit having a specific molecular weight.
  • the present inventors have found that a resin composition obtained by mixing a blend with a coalescent resin with a polycarbonate-based resin can be molded under a wide range of molding conditions and can provide a molded body having excellent surface hardness and transparency. That is, the present invention is as follows, for example.
  • X is a single bond, or —C (R 2 ) (R 3 ) —, —C ( ⁇ O) —, —O—, —OC ( ⁇ O) —, —OC ( ⁇ O) O—, —S
  • R 2 and R 3 are each independently a hydrogen atom, a carbon number of 1
  • [3] The resin composition according to [1] or [2], wherein m is an integer of 1 to 3 in the formula (1).
  • X is a single bond, —C (R 2 ) (R 3 ) —, —C ( ⁇ O) —, —O—, —SO— or —SO 2 —.
  • X is a single bond, —C (R 2 ) (R 3 ) —, —C ( ⁇ O) —, —O—, —SO— or —SO 2 —.
  • X is a single bond, —C (R 2 ) (R 3 ) —, —C ( ⁇ O) —, —SO—, or —SO 2 —;
  • R 1 is a hydrogen atom or a methyl group;
  • R 4 and R 5 are each independently a methyl group, a methoxy group, a chloro group, a bromo group or a phenyl group;
  • m is an integer from 1 to 3;
  • p is an integer from 0 to 1;
  • q is an integer from 0 to 2, [1]
  • [5] The resin composition according to any one of [1] to [4-1], wherein in the formula (1), p and q are 0.
  • [7-1] By melt-kneading the resin composition material according to any one of [1] to [7], and injection molding at an injection temperature of 300 ° C., an injection speed of 300 m / sec, and a mold temperature of 80 ° C.
  • [7-2] The resin composition according to [7-1], wherein the flat specimen has a pencil hardness of HB or higher.
  • X is a single bond, or —C (R 2 ) (R 3 ) —, —C ( ⁇ O) —, —O—, —OC ( ⁇ O) —, —OC ( ⁇ O) O—, —S
  • m is an integer of 1 to 3.
  • X is a single bond, —C (R 2 ) (R 3 ) —, —C ( ⁇ O) —, —O—, —SO— or —SO 2 —.
  • X is a single bond, —C (R 2 ) (R 3 ) —, —C ( ⁇ O) —, —SO—, or —SO 2 —;
  • R 1 is a hydrogen atom or a methyl group;
  • R 4 and R 5 are each independently a methyl group, a methoxy group, a chloro group, a bromo group or a phenyl group;
  • m is an integer from 1 to 3;
  • p is an integer from 0 to 1;
  • q is an integer from 0 to 2, [8]
  • [12] The blend according to any one of [8] to [11-1], wherein in the formula (1), p and q are 0.
  • [12-1] The blend according to any one of [8] to [12], wherein the polymer (B) comprises a methyl methacrylate unit and / or a methyl acrylate unit.
  • the mass ratio ((A) / (B)) between the polymer (A) and the polymer (B) is 0.5 / 99.5 to 30/70 [8] to [12 -1].
  • [14-1] A molded article molded using the resin composition according to any one of [1] to [7].
  • the present invention it is possible to provide a resin composition capable of producing a molded article having excellent surface hardness and transparency under a wide range of molding conditions.
  • the resin composition can be injection-molded at a high speed, productivity is improved.
  • the blend of the some (meth) acrylic-type polymer which comprises the molded article obtained from the said resin composition and the said resin composition can be provided.
  • the resin composition according to the embodiment includes a polymer (A) containing 45% by mass or more of a (meth) acrylate unit (a) represented by the following general formula (1), and a methyl (meth) acrylate unit (b).
  • a polymer (B) containing 60% by mass or more and having a weight average molecular weight of 5,000 to 20,000 and a polycarbonate resin (C) are included.
  • the resin composition of the present embodiment can produce a molded article having excellent surface hardness by containing a (meth) acrylic polymer while maintaining the excellent transparency inherent in the polycarbonate resin. .
  • the molding temperature becomes higher (about 280 ° C. or higher)
  • the injection speed is higher in the case of injection molding.
  • the transparency of the molded product tended to decrease.
  • the resin composition of the present embodiment is molded under a high temperature condition, and in the case of injection molding, a molded article excellent in transparency can be obtained even when the injection speed is high.
  • the reason why a highly transparent molded product can be obtained as described above is not clear, but in the (meth) acrylate unit (a) represented by the general formula (1) described later, the benzene ring of the ester portion is the shape of the molded product. It is thought that it has the effect
  • the (meth) acrylate unit having two or more benzene rings is considered to be excellent in compatibility with the polycarbonate resin (C), so that the transparency of the molded product can be maintained under a wide range of molding conditions. .
  • the reason why the resin composition of the present embodiment has excellent surface hardness is considered to be derived from the fact that a certain amount of methyl (meth) acrylate unit (b), which is excellent in terms of surface hardness, is blended. . This effect is also obtained regardless of the molding conditions. Therefore, according to the resin composition of the present embodiment, a molded product having both high transparency and high surface hardness can be obtained under a wide range of conditions. As a result of obtaining a good molded product under a wide range of conditions, it becomes possible to produce a molded product efficiently and inexpensively.
  • the resin composition of the present embodiment can be used in a wide range of fields such as applications that require transparency such as optical media materials and applications that require color development such as a housing.
  • the polymer (A) which is a constituent component in the resin composition of the present embodiment contains 45% by mass or more of a (meth) acrylate unit (a) represented by the general formula (1) described later. This will be described below.
  • the (meth) acrylate unit (a) is represented by the following general formula (1).
  • the acrylate unit and the methacrylate unit are collectively referred to as a (meth) acrylate unit.
  • the expression “polymer” includes the case of a copolymer.
  • the (meth) acrylate unit (a) represented by the general formula (1) has a structure in which the ester moiety has two or more benzene rings and the oxygen atom of the ester moiety and the benzene ring are not directly bonded. With the above features. Since the (meth) acrylate unit (a) is excellent in compatibility with the polycarbonate-based resin (C), it contributes to an improvement in the transparency of the obtained molded body.
  • R 1 is a hydrogen atom or a methyl group, preferably a methyl group.
  • X is a single bond, or —C (R 2 ) (R 3 ) —, —C ( ⁇ O) —, —O—, —OC ( ⁇ O) —, —OC ( ⁇ O) O—, —S A divalent group selected from the group consisting of —, —SO—, —SO 2 — and any combination thereof, wherein R 2 and R 3 each independently represent a hydrogen atom, a carbon number of 1 to 10 A linear alkyl group, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, A cyclic alkoxy group having 3 to 10 carbon atoms, a phenyl group or a phenylphenyl group.
  • substituents may have a substituent.
  • substituents include a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, and a cyclic alkyl group having 3 to 10 carbon atoms.
  • X is preferably a single bond, —C (R 2 ) (R 3 ) —, —C ( ⁇ O) —, —O—, —SO—, or —SO 2 —, and more preferably a single bond.
  • R 2 and R 3 are preferably each independently selected from a hydrogen atom, a methyl group, a methoxy group, a phenyl group and a phenylphenyl group, and more preferably a hydrogen atom.
  • R 2 and R 3 may be connected to each other to form a cyclic alkyl group having 3 to 10 carbon atoms together with the carbon atom to which they are bonded.
  • R 4 and R 5 are each independently a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a 1 to 10 carbon atom.
  • substituents examples include a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, and a cyclic alkyl group having 3 to 10 carbon atoms.
  • R 4 and R 5 are preferably independently selected from a methyl group, a methoxy group, a chloro group, a bromo group, and a phenyl group, and more preferably a phenyl group.
  • M is an integer of 1 to 10, preferably an integer of 1 to 3, and more preferably 1.
  • P is an integer of 0 to 4, preferably an integer of 0 to 1, more preferably 0.
  • Q is an integer of 0 to 5, preferably an integer of 0 to 2, and more preferably 0.
  • Examples of the (meth) acrylate constituting the (meth) acrylate unit represented by the general formula (1) include 4-phenylbenzyl (meth) acrylate, 3-phenylbenzyl (meth) acrylate, 2-phenylbenzyl ( (Meth) acrylate, 4-biphenylbenzyl (meth) acrylate, 3-biphenylbenzyl (meth) acrylate, 2-biphenylbenzyl (meth) acrylate, 4-benzylbenzyl (meth) acrylate, 3-benzylbenzyl (meth) acrylate, 2 -Benzylbenzyl (meth) acrylate, 4-phenethylbenzyl (meth) acrylate, 3-phenethylbenzyl (meth) acrylate, 2-phenethylbenzyl (meth) acrylate, 4-phenethylphenethyl (meth) acrylate, 3- Enethylphenethyl (
  • the (meth) acrylate unit (a) represented by the general formula (1) with respect to all the structural units of the polymer (A) is 45% by mass or more, preferably It is contained in a proportion of 50% by mass or more, more preferably 60% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more.
  • the polymer (A) needs to be added in order to improve the compatibility between the polymer (B) and the polycarbonate resin (C), which will be described later.
  • proportion of (meth) acrylate units (a) is 45% by mass or more, preferably It is contained in a proportion of 50% by mass or more, more preferably 60% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more.
  • the proportion of the (meth) acrylate unit (a) in the polymer (A) is preferably 45 to 99% by mass, more preferably 50 to 99% by mass, and 60 to 97% by mass. It is particularly preferred.
  • the proportion of the (meth) acrylate unit (a) in the polymer (A) is 45% by mass or more, the compatibility between the polymer (B) and the polycarbonate resin (C) is sufficiently improved, and the polycarbonate resin The transparency of (C) is maintained.
  • other monomers described later may be copolymerized, so that the proportion of the (meth) acrylate unit (a) in the polymer (A) is 99% by mass or less. Is preferred.
  • the polymer (A) further contains 55 mass% or less, preferably 50 mass% or less, more preferably a structural unit derived from another monomer (hereinafter sometimes referred to as component (c)). May be produced by copolymerization at a ratio of 40% by mass or less, particularly preferably 20% by mass or less, and most preferably 10% by mass or less.
  • component (c) is not particularly limited as long as it does not adversely affect the properties of the resin composition.
  • methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, propyl methacrylate, and 2-ethylhexyl methacrylate
  • methyl acrylate, ethyl acrylate, Acrylates such as butyl acrylate, propyl acrylate, 2-ethylhexyl acrylate and glycidyl acrylate
  • vinyl cyanide monomers such as acrylonitrile and methacrylonitrile
  • diene monomers such as butadiene, isoprene and dimethylbutadiene
  • vinyl methyl ether and vinyl Vinyl ether monomers such as ethyl ether
  • Carboxylic acid vinyl monomers such as vinyl acetate and vinyl butyrate
  • Olefins such as ethylene, propylene and isobutylene Monomer
  • ethylenically unsaturated carboxylic acid monomer such as acrylic acid, methacrylic acid
  • the structural unit derived from the component (c) is based on the polymer (A).
  • the content is preferably 0.1 to 5% by mass, more preferably 0.5 to 4% by mass, and particularly preferably 1 to 3% by mass.
  • the mass average molecular weight of the polymer (A) is preferably 50,000 to 5,000,000, more preferably 80,000 to 3,000,000, and particularly preferably 100,000 to 2,000,000.
  • the weight average molecular weight is 50,000 to 5,000,000, the compatibility with the polycarbonate resin (C) is good, which is preferable from the viewpoint of mechanical properties and surface hardness.
  • the polymerization method for obtaining the polymer (A) in the present embodiment is not particularly limited.
  • a known method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, or a bulk polymerization method may be used. it can.
  • a suspension polymerization method and a bulk polymerization method are preferable, and a suspension polymerization method is more preferable.
  • additives necessary for the polymerization can be appropriately added as necessary, and examples of the additive include a polymerization initiator, an emulsifier, a dispersant, and a chain transfer agent.
  • the polymerization temperature varies depending on the structure and composition of the monomer to be polymerized and additives such as a polymerization initiator, but is preferably 50 ° C. to 150 ° C., more preferably 70 ° C. to 130 ° C.
  • the polymerization may be performed by raising the temperature in multiple stages.
  • the polymerization time varies depending on the polymerization method, the structure and composition of the monomer to be polymerized, and additives such as a polymerization initiator, but is preferably 1 hour to 8 hours, more preferably 2 hours to 6 hours at the target temperature. In addition, the time until the temperature is raised to the target temperature is further added to the polymerization time.
  • the reaction pressure varies depending on the polymerization method, the structure and composition of the monomer to be polymerized, etc., but the polymerization is preferably carried out at 0 MPa (normal pressure) to 3 MPa, more preferably 0 MPa (normal pressure) to 1 MPa.
  • the polymer (B) in this embodiment contains 60% by mass or more of methyl (meth) acrylate units (b) and has a weight average molecular weight of 5,000 to 20,000.
  • the content of the methyl (meth) acrylate unit (b) with respect to all the structural units of the polymer (B) is 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and 95% by mass or more. Is more preferable.
  • the upper limit of the content of the methyl (meth) acrylate unit (b) in the polymer (B) is preferably 99.5% by mass or less, and more preferably 99% by mass or less.
  • the polymer (B) is preferably composed only of methyl (meth) acrylate units (b) except for structural units derived from additives such as chain transfer agents, and a combination of methyl methacrylate units and methyl acrylate units. It is most preferable that it is comprised only by.
  • the polymer (B) contains constituent units derived from other monomers in an amount of 40% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less. May be.
  • the structural unit derived from the other monomer may be a structural unit derived from a monomer copolymerizable with methyl (meth) acrylate, and is derived from an ⁇ , ⁇ -unsaturated monomer. Is preferred.
  • Examples of such monomers include alkyl methacrylates such as ethyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate; alkyl acrylates such as ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate; phenyl methacrylate, benzyl methacrylate, phenyl acrylate and benzyl acrylate Aromatic vinyl (meth) acrylates; aromatic vinyl compounds such as styrene, ⁇ -methylstyrene and vinyltoluene; and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. These may be used alone or in combination of two or more.
  • alkyl acrylates such as ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate, and styrene are preferable.
  • the mass average molecular weight (Mw) of the polymer (B) is 5,000 or more, preferably 7,000 or more, more preferably 9,000 or more.
  • Mw of the polymer (B) When the Mw of the polymer (B) is 5,000 or more, excellent surface hardness can be obtained in the obtained molded product. If Mw of a polymer (B) is less than 5,000, since the glass transition temperature of a polymer (B) will fall, the improvement effect of surface hardness may fall in the molded article obtained.
  • the Mw of the polymer (B) is 20,000 or less, preferably 18,000 or less, more preferably 13,000 or less, and most preferably 10,000 or less.
  • Mw of the polymer (B) is 20,000 or less, the compatibility with the polycarbonate (C) is good, and the effect of improving the surface hardness is excellent.
  • the polymerization method for obtaining the polymer (B) is not particularly limited, and known methods such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a bulk polymerization method can be used.
  • a suspension polymerization method and a bulk polymerization method are preferable, and a suspension polymerization method is more preferable.
  • additives necessary for the polymerization can be appropriately added as necessary, and examples of the additive include a polymerization initiator, an emulsifier, a dispersant, and a chain transfer agent.
  • the polymerization temperature varies depending on the structure and composition of the monomer to be polymerized and additives such as a polymerization initiator, but is preferably 50 ° C. to 150 ° C., more preferably 70 ° C. to 130 ° C.
  • the polymerization may be performed by raising the temperature in multiple stages.
  • the polymerization time varies depending on the polymerization method, the structure and composition of the monomer to be polymerized, and additives such as a polymerization initiator, but is preferably 1 hour to 8 hours, more preferably 2 hours to 6 hours at the target temperature. In addition, the time until the temperature is raised to the target temperature is further added to the polymerization time.
  • the reaction pressure varies depending on the polymerization method, the structure and composition of the monomer to be polymerized, etc., but the polymerization is preferably carried out at 0 MPa (normal pressure) to 3 MPa, more preferably 0 MPa (normal pressure) to 1 MPa.
  • the polycarbonate resin (C) is not particularly limited as long as it contains a carbonate bond in the molecular main chain, that is, has a — [O—R—OCO] — unit.
  • R in the formula may be an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group.
  • an aromatic polycarbonate obtained using an aromatic dihydroxy compound such as bisphenol A is preferable from the viewpoint of cost.
  • these polycarbonate-type resin can be used individually by 1 type or in combination of 2 or more types.
  • the viscosity average molecular weight (Mv) of the polycarbonate resin (C) can be calculated by a viscosity method, and is preferably 15,000 to 30,000, more preferably 17,000 to 25,000. . If the viscosity average molecular weight is in the above range, the compatibility with the polymer (A) and the polymer (B) in this embodiment is good, and a molded product having more excellent transparency and surface hardness can be obtained.
  • the resin composition of the present embodiment contains the polymer (A), the polymer (B), and the polycarbonate resin (C).
  • the resin composition of this embodiment contains 5 to 60% by mass of a (meth) acrylic polymer obtained by combining the polymer (A) and the polymer (B) based on the mass of the resin composition.
  • the polycarbonate resin (C) is preferably contained in an amount of 40 to 95% by mass.
  • the resin composition of the present embodiment contains 10 to 50% by mass of a (meth) acrylic polymer obtained by combining the polymer (A) and the polymer (B), and a polycarbonate resin (C). Is more preferably contained in an amount of 50 to 90% by mass.
  • the content of the (meth) acrylic polymer in which the polymer (A) and the polymer (B) in the resin composition are combined is 5% by mass or more, compatibility with the polycarbonate resin (C) And improvement of fluidity can be achieved.
  • the haze tends to increase even if the content of the (meth) acrylic polymer in which the polymer (A) and the polymer (B) are combined is too much, the polymer (A) and the polymer ( When the content of the (meth) acrylic polymer combined with B) is 60% by mass or less, it is possible to suppress a decrease in transparency of the obtained molded body.
  • the mass ratio ((A) / (B)) of the polymer (A) to the polymer (B) is 0.5 / The range is preferably 99.5 to 30/70, more preferably 2/98 to 25/75, and still more preferably 5/95 to 20/80. If the polymer (A) is 0.5% by mass or more in the mass ratio ((A) / (B)) between the polymer (A) and the polymer (B), compatibility with the polycarbonate is improved. Can do. On the other hand, if the polymer (B) is 70% by mass or more in the mass ratio ((A) / (B)) between the polymer (A) and the polymer (B), sufficient surface hardness can be improved. Can do.
  • the resin composition of the present embodiment may contain other resins, additives, and the like as necessary within a range that does not impair the effects of the present invention.
  • polystyrene resins such as ABS, HIPS, PS, and PAS
  • polyester resins such as polyethylene terephthalate and polybutylene terephthalate
  • polyolefin resins such as polyethylene terephthalate and polybutylene terephthalate
  • polyolefin resins such as polyethylene terephthalate and polybutylene terephthalate
  • polyolefin resins such as polystyrenephthalate
  • other thermoplastic resins are blended.
  • examples thereof include polymer alloys such as elastomers.
  • the content of these resins is preferably in a range that does not impair the physical properties of the polycarbonate resin (C) such as heat resistance, impact resistance, flame retardancy, and specifically, the polymer (A) and It is preferable that it is 50 mass parts or less with respect to a total of 100 mass parts of a polymer (B) and a polycarbonate-type resin (C).
  • the additive is not particularly limited.
  • a reinforcing agent in addition to an ultraviolet absorber and an antioxidant described later, a reinforcing agent, a weathering agent, an inorganic filler, an impact modifier, a flame retardant, an antistatic agent, a release agent, and the like. Mention may be made of mold agents, dyes and pigments, and fluoroolefins. Further, talc, mica, calcium carbonate, glass fiber, carbon fiber, potassium titanate fiber, etc. can be used to improve the strength, rigidity, flame retardancy, etc. of the molded body. Furthermore, you may contain the rubber-like elastic body which consists of a core-shell two-layer structure for improving impact resistance.
  • the resin composition of the present embodiment may contain an ultraviolet absorber.
  • the ultraviolet absorber used in the present embodiment include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, and ogizanides.
  • examples thereof include organic ultraviolet absorbers such as compounds, malonic acid ester compounds, hindered amine compounds, and oxalic acid anilide compounds.
  • an organic ultraviolet absorber is preferable, and a benzotriazole compound (a compound having a benzotriazole structure) is more preferable.
  • benzotriazole compound examples include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis ( ⁇ , ⁇ -dimethyl).
  • Benzyl) phenyl] -benzotriazole 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5) '-Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'-hydroxy- 3 ′, 5′-di-tert-amyl) -benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole 2,2'-methylenebis [4- (1,1,1,
  • benzotriazole-based compounds examples include “Seasorb 701”, “Seesorb 705”, “Seesorb 703”, “Seesorb 702”, “Seesorb 704”, and “Seesorb 709” manufactured by Sipro Kasei Co., Ltd. “Biosorb 520”, “Biosorb 582”, “Biosorb 580”, “Biosorb 583”, Chemipro Chemical Co., Ltd.
  • benzophenone compounds include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octate.
  • benzophenone compounds examples include “Seasorb 100”, “Seesorb 101”, “Seesorb 101S”, “Seesorb 102”, and “Seesorb 103” manufactured by Sipro Kasei Co., Ltd. "Kyodo Pharmaceutical Co., Ltd. “Biosorb 100”, “Biosorb 110”, “Biosorb 130”, “Chemisorb 10”, “Chemsorb 11”, “Chemsorb 11S”, “Chemsorb 12”, “Chemsorb 13”, “Chemsorb 111”, BASF manufactured by Chemipro Kasei Co., Ltd.
  • salicylate compounds include phenyl salicylate, 4-tert-butylphenyl salicylate, and the like.
  • examples of such salicylate compounds include “Seasorb 201” and “Seasorb 202” manufactured by Sipro Kasei Co., Ltd. Chemipro Kasei Co., Ltd. “Chemisorb 21”, “Chemisorb 22” and the like.
  • cyanoacrylate compound examples include, for example, ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like.
  • examples of such products include “Seasorb 501” manufactured by Sipro Kasei Co., Ltd., “Biosorb 910” manufactured by Kyodo Yakuhin Co., Ltd., “Ubisolator 300” manufactured by Daiichi Kasei Co., Ltd., “Ubinur N-35”, “Ubinur N-539” manufactured by BASF, etc. Is mentioned.
  • oxanilide compound examples include, for example, 2-ethoxy-2′-ethyl oxalinic acid bis-arinide.
  • examples of such oxalinide compound include “Sanduboa VSU” manufactured by Clariant. Etc.
  • malonic acid ester compound 2- (alkylidene) malonic acid esters are preferable, and 2- (1-arylalkylidene) malonic acid esters are more preferable.
  • examples of such a malonic ester compound include “PR-25” manufactured by Clariant Japan, “B-CAP” manufactured by Ciba Specialty Chemicals, and the like.
  • the blending amount of the ultraviolet absorber used in the present embodiment is 0.05 to 100 parts by mass with respect to 100 parts by mass of the resin component containing the polymer (A), the polymer (B) and the polycarbonate resin (C).
  • the amount is 2.0 parts by mass, more preferably 0.1 to 1.5 parts by mass, and still more preferably 0.2 to 1.0 parts by mass. If the blending amount is 0.05 parts by mass or more, sufficient weather resistance tends to be exhibited, and if it is 2.0 parts by mass or less, the amount of outgas at the time of molding can be suppressed, and mold contamination This problem tends not to occur.
  • only 1 type may contain the ultraviolet absorber and 2 or more types may contain it by arbitrary combinations and a ratio.
  • the resin composition of the present embodiment may contain an antioxidant.
  • the antioxidant used in the present embodiment include phenol-based antioxidants, amine-based antioxidants, phosphite-based antioxidants, and thioether-based antioxidants. 1 type may contain antioxidant and 2 or more types may contain it by arbitrary combinations and a ratio. Among these, the use of a phenolic antioxidant or the combined use of a phenolic antioxidant and a phosphite antioxidant is preferred.
  • phenolic antioxidants include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl).
  • pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable.
  • a phenolic antioxidant include “Irganox 1010” and “Irganox 1076” manufactured by Ciba, “Adekastab AO-50”, “Adekastab AO-60” manufactured by Adeka, and the like.
  • phosphite antioxidant examples include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, Tris (tridecyl) phosphite, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra (tridecyl) pentaerythritol Tetraphosphite, hydrogenated bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite polymer
  • amine antioxidants include poly (2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, phenyl- ⁇ -naphthylamine, 4,4-bis ( ⁇ , ⁇ -dimethyldendyl) diphenylamine, (p-toluenesulfonylamido) diphenylamine, N, N′-diphenyl-p-phenylenediamine, N, N′-di- ⁇ - Naphthyl-p-phenylenediamine, N, N′-di (1,4-dimethylpentyl) -p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, N-phenyl-N′-1, Aromatic amines such as 3-dimethylbutyl-p-phenylenediamine and N- (1-methylheptyl)
  • thioether-based antioxidant examples include pentaerythrityl tetrakis (3-lauryl thiopropionate), dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, di And stearyl-3,3′-thiodipropionate.
  • the compounding amount of the antioxidant is 0.01 to 1.0 part by mass with respect to 100 parts by mass of the resin component containing the polymer (A), the polymer (B) and the polycarbonate resin (C). More preferably, it is 0.05 to 0.8 parts by mass, and still more preferably 0.1 to 0.5 parts by mass. If the content of the antioxidant is 0.01 parts by mass or more, a sufficient effect as an antioxidant tends to be exhibited, and if the content of the antioxidant is 1.0 parts by mass or less, the effect It tends to be economical because it can suppress excessive addition due to the peak of the amount.
  • the resin composition of the present embodiment is a method of blending the polymer (A), the polymer (B), and the polycarbonate resin (C) in a powder state, or a method of blending by heating and melting them. Can be manufactured. Further, the resin composition of the present embodiment is obtained by blending the polymer (A) and the polymer (B) in a powder state, or blending them by heating and melting them, and further, the polycarbonate resin. It can be produced by adding (C) in a powder state and blending, or heating and melting and blending.
  • a Henschel mixer for the production of the blend, for example, a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, two rolls, a kneader, a Brabender, or the like can be used.
  • a blend of the polymer (A) and the polymer (B) can be provided. That is, the blend of this embodiment comprises a polymer (A) containing 45% by mass or more of a (meth) acrylate unit (a) represented by the formula (1) and a methyl (meth) acrylate unit (b). And a polymer (B) having a mass average molecular weight of 5,000 to 20,000.
  • the mass ratio ((A) / (B)) of the polymer (A) to the polymer (B) in the blend is 0.5 / The range is preferably 99.5 to 30/70, more preferably 2/98 to 25/75, and still more preferably 5/95 to 20/80. If the polymer (A) is 0.5% by mass or more in the mass ratio ((A) / (B)) between the polymer (A) and the polymer (B), compatibility with the polycarbonate is improved. Can do. On the other hand, if the polymer (B) is 70% by mass or more in the mass ratio ((A) / (B)) between the polymer (A) and the polymer (B), sufficient surface hardness can be improved. Can do.
  • the blend of this embodiment may contain the above-described other resins, additives, and the like as necessary within a range that does not impair the effects of the present invention.
  • the blend of this embodiment can be produced by a method of blending the polymer (A) and the polymer (B) in a powder state, or a method of blending them by heating and melting them.
  • a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a two-roll, a kneader, a Brabender, or the like can be used.
  • the molded body according to the embodiment is obtained by molding the resin composition.
  • a blend of the polymer (A) and the polymer (B) and a polycarbonate resin (C) (viscosity average molecular weight: 22,000) are melt-kneaded at a ratio of 30/70 (mass%), and injection is performed.
  • the haze of a 1.5 mm-thick flat plate test piece obtained by injection molding at a temperature of 300 ° C., an injection speed of 300 m / sec, and a mold temperature of 80 ° C. is preferably 12% or less, and 10% or less. More preferably, it is particularly preferably 5% or less.
  • the pencil hardness of the said flat test piece is HB or more, and it is more preferable that it is F or more.
  • the molded product of the present embodiment maintains the excellent mechanical strength, heat resistance, electrical properties, dimensional stability, flame retardancy, transparency and the like of the polycarbonate resin (C), and The surface hardness is excellent. Therefore, the molded body of the present embodiment can be used for electrical and electronic equipment, OA equipment, optical media, automobile parts, building members, and the like.
  • Examples of the molding method of the molded body of the present embodiment include compression molding, transfer molding, injection molding, blow molding, extrusion molding, laminate molding, and calendar molding.
  • the injection molding conditions are that the injection temperature is 230 to 330 ° C., the injection speed is 10 to 500 mm / sec, and the mold temperature is 60 ° C. or more from the viewpoint of improving surface hardness. preferable.
  • the resin composition of this embodiment since it is possible to make an injection speed high, it is preferable also from a viewpoint of productivity.
  • Parts and “%” in Examples and Comparative Examples represent “parts by mass” and “% by mass”, respectively.
  • Synthesis of Polymer (A) ⁇ Synthesis Example 1 Synthesis of Polymer (A) -a> 200 parts by mass of deionized water, 0.5 part by mass of calcium triphosphate as a suspension stabilizer, 0.01% sodium dodecylbenzenesulfonate as a surfactant in a high-pressure reactor capable of heating equipped with a stirrer After adding a mass part, it stirred.
  • Synthesis of polymer (A) -c> A polymer (A) -c was obtained in the same manner as in Synthesis Example 2, except that 50 parts by mass of 4-phenylbenzyl methacrylate and 47 parts by mass of methyl methacrylate were used.
  • Synthesis of polymer (A) -f> A polymer (A) -f was obtained in the same manner as in Synthesis Example 1 except that 45 parts by mass of 4-phenylbenzyl methacrylate and 52 parts by mass of methyl methacrylate were used.
  • Synthesis of polymer (A) -g> A polymer (A) -g was obtained in the same manner as in Synthesis Example 1, except that 2-phenylbenzyl methacrylate was used instead of 4-phenylbenzyl methacrylate.
  • Synthesis of Polymer (A) -j> A polymer (A) -j was obtained in the same manner as in Synthesis Example 1, except that 4- (phenylsulfonyl) benzyl methacrylate was used instead of 4-phenylbenzyl methacrylate.
  • Table 1 summarizes the compositions of the polymers obtained in Synthesis Examples 1 to 14 (the values in Table 1 are mass ratios).
  • Table 2 summarizes the physical properties of the polymers obtained in Synthesis Examples 1-14.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

Selon un mode de réalisation, l'invention concerne une composition de résine comprenant un polymère (A) qui comprend 45 % en masse ou plus d'unités (méth)acrylate (a), représenté par la formule suivante (1), un polymère (B) qui comprend 60 % en masse ou plus d'unités méthyl(méth)acrylate (b) et a un poids moléculaire moyen en masse de 5000 à 20000, et une résine à base de polycarbonate (C).
PCT/JP2016/057887 2015-03-30 2016-03-14 Composition de résine et objet moulé obtenu à partir de celle-ci WO2016158332A1 (fr)

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EP16772215.6A EP3279259A4 (fr) 2015-03-30 2016-03-14 Composition de résine et objet moulé obtenu à partir de celle-ci
JP2016551328A JP6112264B2 (ja) 2015-03-30 2016-03-14 樹脂組成物及びこれを用いた成形体
US15/535,580 US10150865B2 (en) 2015-03-30 2016-03-14 Resin composition and molded object obtained therefrom
KR1020177023343A KR101898108B1 (ko) 2015-03-30 2016-03-14 수지 조성물 및 이것을 이용한 성형체

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JPWO2016158332A1 (ja) 2017-04-27
KR20170100051A (ko) 2017-09-01
TWI619758B (zh) 2018-04-01
KR101898108B1 (ko) 2018-09-12
CN107406654B (zh) 2019-03-08
US20170327685A1 (en) 2017-11-16
US10150865B2 (en) 2018-12-11
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